Biocide compositions (I)

ABSTRACT

Suggested are biocide compositions, comprising
         (a) at least one dialkylamide based on a hydroxycarboxylic acid, and   (b) at least one biocide.       

     The compositions exhibit an improved stability even if stored at temperatures between 5° and 40° C. over a longer period.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is the National Phase entry of PCT/EP2008/001081, filed Feb. 13, 2008 which claims priority to EPO patent application number 07003635 filed Feb. 22, 2007 both of which are incorporated herein by reference in their entireties.

FIELD OF THE INVENTION

The present invention relates to the area of agrochemnicals and refers to biocide compositions comprising certain dialkylamides, and to the use of such dialkylamides as solvents or dispersants for biocides.

BACKGROUND OF THE INVENTION

Biocides, and in particular pesticides such as fungicides, insecticides and herbicides, are important auxiliary agents for agriculture in order to protect and to increase the yield of crops. Depending on the various and often very specific needs, a number of actives exist, which show very different chemical structures and behaviours. Nevertheless, it is well known from the state of the art that it remains difficult to prepare aqueous solutions of these actives exhibiting a satisfactory stability, especially if stored over a longer time at very low or elevated temperatures. As a matter of fact, the solutions show a strong tendency to either separate or form crystals, which makes it necessary to re-disperse the actives in the compositions prior to every application in order to obtain a homogenous product. Due to the fact that in spray equipments, which is customarily used for the application of aqueous formulations of plant treatment agents, several filters and nozzles are present, an additional problem appears which is related to the blocking of these filters and nozzles as a result of crystallizing active compound during the application of aqueous spray liquors based on solid active ingredients.

European patent application EP 0453899 B1 (Bayer) discloses the use of dimethylamides derived from saturated C₆-C₂₀ fatty acids as crystallisation inhibitors for azol derivatives which can be applied as fungicides. Unfortunately, the dimethylamides suggested in the patent are useful for a limited number of actives. Even in case of azols and azol derivatives the ability to inhibit unwanted crystallisation is limited to ambient temperatures, while the products are close to being useless in case the solutions have to be used at temperatures of about 5 to 10° C.

Therefore the problem underlying the present invention has been to avoid the disadvantages of the state of the art and develop new compositions with improved storage stability and reduced tendency to form crystals for a wide range of biocides within a temperature range between 5 and 40° C.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention refers to biocide compositions, comprising

-   -   (a) at least one dialkylamide based on a hydroxycarboxylic acid,         and     -   (b) at least one biocide.

Surprisingly it has been observed that dialkylamides, and preferably dimethylamides, obtained from hydroxycarboxylic acid, in particular lactic acid dimethylamide, show an improved solubilising power compared to dimethylamides from fatty acids as known from the state of the art. Applicant has found that the hydroxycarboxylic acid dialkylamides are able to dissolve or disperse a wide range of biocides even under drastic conditions, which means storage times of at least 4 weeks at temperatures between 5 and 40° C. without phase separation or sedimentation.

Dialkylamides

Dialkylamides according to the present invention (component a) can be derived from hydroxy-substituted mono-, di- or tricarboxylic acid. In case the carboxylic acid has two or three acid groups, the amide may be a mono-, di- or triamide or represent a statistical mixture. In a first embodiment of the present invention, dialkylamides follow the general formula (I), R¹CO—NR²R³  (I) in which R¹CO stands for a hydroxysubstituted acyl radical having 2 to 22 carbon atoms, and R² and R³ independently represent hydrogen or alkyl groups having 1 to 4 carbon atoms. Typical examples are dialkylamides of lactic acid, ricinoleic acid or 12-hydroxy stearic acid. Other suitable dialkylamides can be derived from citric acid or tartaric acid or their mixtures. The preferred dialkylamides represent dimethylamides. The most preferred species exhibiting the best performance in dissolving or dispersing a wide number of different biocides over a long period and both at low and high temperatures is lactic acid dimethylamide. Biocides

A biocide (component b) is a chemical substance capable of killing different forms of living organisms used in fields such as medicine, agriculture, forestry, and mosquito control. Usually, biocides are divided into two sub-groups:

-   -   pesticides, which includes fungicides, herbicides, insecticides,         algicides, moluscicides, miticides and rodenticides, and     -   antimicrobials, which includes germicides, antibiotics,         antibacterials, antivirals, antifungals, antiprotozoals and         antiparasites.

Biocides can also be added to other materials (typically liquids) to protect the material from biological infestation and growth. For example, certain types of quaternary ammonium compounds (quats) can be added to pool water or industrial water systems to act as an algicide, protecting the water from infestation and growth of algae.

Pesticides

The U.S Environmental Protection Agency (EPA) defines a pesticide as “any substance or mixture of substances intended for preventing, destroying, repelling, or mitigating any pest”.^([1]) A pesticide may be a chemical substance or biological agent (such as a virus or bacteria) used against pests including insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms) and microbes that compete with humans for food, destroy property, spread disease or are a nuisance. In the following examples, pesticides suitable for the agrochemical compositions according to the present invention are given:

Fungicides

-   -   A fungicide is one of three main methods of pest control—the         chemical control of fungi in this case. Fungicides are chemical         compounds used to prevent the spread of fungi in gardens and         crops. Fungicides are also used to fight fungal infections.         Fungicides can either be contact or systemic. A contact         fungicide kills fungi when sprayed on its surface. A systemic         fungicide has to be absorbed by the fungus before the fungus         dies. Examples for suitable fungicides, according to the present         invention, encompass the following species:         (3-ethoxypropyl)mercury bromide, 2-methoxyethylmercury chloride,         2-phenylphenol, 8-hydroxyquinoline sulfate,         8-phenylmercurioxyquinoline, acibenzolar, acylamino acid         fungicides, acypetacs, aldimorph, aliphatic nitrogen fungicides,         allyl alcohol, amide fungicides, ampropylfos, anilazine, anilide         fungicides, antibiotic fungicides, aromatic fungicides,         aureofungin, azaconazole, azithiram, azoxystrobin, barium         polysulfide, benalaxy,l benalaxyl-M, benodanil, benomyl,         benquinox, bentaluron, benthiavalicarb, benzalkonium chloride,         benzamacril, benzamide fungicides, benzamorf, benzanilide         fungicides, benz imidazole fungicides, benzimidazole precursor         fungicides, benzimidazolylcarbamate fungicides, benzohydroxamic         acid, benzothiazole fungicides, bethoxazin, binapacryl,         biphenyl, bitertanol, bithionol, blasticidin-S, Bordeaux         mixture, boscalid, bridged diphenyl fungicides, bromuconazole,         bupirimate, Burgundy mixture, buthiobate, butylamine, calcium         polysulfide, captafol, captan, carbamate fungicides, carbamorph,         carbanilate fungicides, carbendazim, carboxin, carpropamid,         carvone, Cheshunt mixture, chinomethionat, chlobenthiazone,         chloraniformethan, chloranil, chlorfenazole,         chlorodinitronaphthalene, chloroneb, chloropicrin,         chlorothalonil, chlorquinox, chlozolinate, ciclopirox,         climbazole, clotrimazole, conazole fungicides, conazole         fungicides (imidazoles), conazole fungicides (triazoles),         copper(II) acetate, copper(II) carbonate, basic, copper         fungicides, copper hydroxide, copper naphthenate, copper oleate,         copper oxychloride, copper(II) sulfate, copper sulfate, basic,         copper zinc chromate, cresol, cufraneb, cuprobam, cuprous oxide,         cyazofamid, cyclafuramid, cyclic dithiocarbamate fungicides,         cycloheximide, cyflufenamid, cymoxanil, cypendazole,         cyproconazole, cyprodinil, dazomet, DBCP, debacarb, decafentin,         dehydroacetic acid, dicarboximide fungicides, dichlofluanid,         dichlone, dichlorophen, dichlorophenyl, dicarboximide         fungicides, dichlozoline, diclobutrazol, diclocymet,         diclomezine, dicloran, diethofencarb, diethyl pyrocarbonate,         difenoconazole, diflumetorim, dimethirimol, dimethomorph,         dimoxystrobin, diniconazole, dinitrophenol fungicides,         dinobuton, dinocap, dinocton, dinopenton, dinosulfon,         dinoterbon, diphenylamine, dipyrithione, disulfuram, ditalimfos,         dithianon, dithiocarbamate fungicides, DNOC, dodemorph, dodicin,         dodine, DONATODINE, drazoxolon, edifenphos, epoxiconazole,         etaconazole, etem, ethaboxam, ethirimol, ethoxyquin,         ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury         acetate, ethylmercury bromide, ethylmercury chloride,         ethylmercury phosphate, etridiazole, famoxadone, fenamidone,         fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram,         fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpropidin,         fenpropimorph, fentin, ferbam, ferimzone, fluazinam,         fludioxonil, flumetover, flumorph, fluopicolide, fluoroimide,         fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole,         flusulfamide, flutolanil, flutriafol, folpet, formaldehyde,         fosetyl, fuberidazole, furalaxyl, furametpyr, furamide         fungicides, furanilide fungicides, furcarbanil, furconazole,         furconazole-cis, furfural, furmecyclox, furophanate, glyodin,         griseofulvin, guazatine, halacrinate, hexachlorobenzene,         hexachlorobutadiene, hexachlorophene, hexaconazole,         hexylthiofos, hydrargaphen, hymexazol, imazalil, imibenconazole,         imidazole fungicides, iminoctadine, inorganic fungicides,         inorganic mercury fungicides, iodomethane, ipconazole,         iprobenfos, iprodione, iprovalicarb, isoprothiolane,         isovaledione, kasugamycin, kresoxim-methyl, lime sulphur,         mancopper, mancozeb, maneb, mebenil, mecarbinzid, mepanipyrim,         mepronil, mercuric chloride, mercuric oxide, mercurous chloride,         mercury fungicides, metalaxyl, metalaxyl-M, metam, metazoxolon,         metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl         isothiocyanate, methylmercury benzoate, methylmercury         dicyandiamide, methylmercury pentachlorophenoxide, metiram,         metominostrobin, metrafenone, metsulfovax, milneb, morpholine         fungicides, myclobutanil, myclozolin,         N-(ethylmercury)-p-toluenesulphonanilide, nabam, natamycin,         nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone,         ofurace, organomercury fungicides, organophosphorus fungicides,         organotin fungicides, orysastrobin, oxadixyl, oxathiin         fungicides, oxazole fungicides, oxine copper, oxpoconazole,         oxycarboxin, pefurazoate, penconazole, pencycuron,         pentachlorophenol, penthiopyrad, phenylmercuriurea,         phenylmercury acetate, phenylmercury chloride, phenylmercury         derivative of pyrocatechol, phenylmercury nitrate, phenylmercury         salicylate, phenylsulfamide fungicides, phosdiphen, phthalide,         phthalimide fungicides, picoxystrobin, piperalin, polycarbamate,         polymeric dithiocarbamate fungicides, polyoxins, polyoxorim,         polysulfide fungicides, potassium azide, potassium polysulfide,         potassium thiocyanate, probenazole, prochloraz, procymidone,         propamocarb, propiconazole, propineb, proquinazid, prothiocarb,         prothioconazole, pyracarbolid, pyraclostrobin, pyrazole         fungicides, pyrazophos, pyridine fungicides, pyridinitril,         pyrifenox, pyrimethanil, pyrimidine fungicides, pyroquilon,         pyroxychlor, pyroxyfur, pyrrole fungicides, quinacetol,         quinazamid, quinconazole, quinoline fungicides, quinone         fungicides, quinoxaline fungicides, quinoxyfen, quintozene,         rabenzazole, salicylanilide, silthiofam, simeconazole, sodium         azide, sodium orthophenylphenoxide, sodium pentachlorophenoxide,         sodium polysulfide, spiroxamine, streptomycin, strobilurin         fungicides, sulfonanilide fungicides, sulfur, sultropen, TCMTB,         tebuconazole, tecloftalam, tecnazene, tecoram, tetraconazole,         thiabendazole, thiadifluor, thiazole fungicides, thicyofen,         thifluzamide, thiocarbamate fungicides, thiochlorfenphim,         thiomersal, thiophanate, thiophanate-methyl, thiophene         fungicides, thioquinox, thiram, tiadinil, tioxymid, tivedo,         tolclofos-methyl, tolnaftate, tolylfluanid, tolylmercury         acetate, triadimefon, triadimenol, triamiphos, triarimol,         triazbutil, triazine fungicides, triazole fungicides,         triazoxide, tributyltin oxide, trichlamide, tricyclazole,         tridemorph, trifloxystrobin, triflumizole, triforine,         triticonazole, unclassified fungicides, undecylenic acid,         uniconazole, urea fungicides, validamycin, valinamide         fungicides, vinclozolin, zarilamid, zinc naphthenate, zineb,         ziram, zoxamide and their mixtures.

Herbicides

-   -   An herbicide is a pesticide used to kill unwanted plants.         Selective herbicides kill specific targets while leaving the         desired crop relatively unharmed. Some of these act by         interfering with the growth of the weed and are often based on         plant hormones. Herbicides used to clear waste ground are         nonselective and kill all plant material with which they come         into contact. Herbicides are widely used in agriculture and in         landscape turf management. They are applied in total vegetation         control (TVC) programs for maintenance of highways and         railroads. Smaller quantities are used in forestry, pasture         systems, and management of areas set aside as wildlife habitat.         In the following, a number of suitable herbicides are compiled:         -   2,4-D, a broadleaf herbicide in the phenoxy group used in             turf and in no-till field crop production. Now mainly used             in a blend with other herbicides that act as synergists, it             is the most widely used herbicide in the world, third most             commonly used in the United States. It is an example of             synthetic auxin (plant hormone).         -   Atrazine, a triazine herbicide used in corn and sorghum for             control of broadleaf weeds and grasses. It is still used             because of its low cost and because it works as a synergist             when used with other herbicides, it is a photosystem II             inhibitor.         -   Clopyralid, a broadleaf herbicide in the pyridine group,             used mainly in turf, rangeland, and for control of noxious             thistles. Notorious for its ability to persist in compost.             It is another example of synthetic auxin.         -   Dicamba, a persistent broadleaf herbicide active in the             soil, used on turf and field corn. It is another example of             synthetic auxin.         -   Glyphosate, a systemic nonselective (it kills any type of             plant) herbicide used in no-till burndown and for weed             control in crops that are genetically modified to resist its             effects. It is an example of a EPSPs inhibitor.         -   Imazapyr, a non-selective herbicide used for the control of             a broad range of weeds including terrestrial annual and             perennial grasses and broadleaved herbs, woody species, and             riparian and emergent aquatic species.         -   Imazapic, a selective herbicide for both the pre- and             post-emergent control of some annual and perennial grasses             and some broadleaf weeds. Imazapic kills plants by             inhibiting the production of branched chain amino acids             (valine, leucine, and isoleucine), which are necessary for             protein synthesis and cell growth.         -   Metoalachlor, a pre-emergent herbicide widely used for             control of annual grasses in corn and sorghum; it has             largely replaced atrazine for these uses.         -   Paraquat, a nonselective contact herbicide used for no-till             burndown and in aerial destruction of marijuana and coca             plantings. More acutely toxic to people than any other             herbicide in widespread commercial use.         -   Picloram, a pyridine herbicide mainly used to control             unwanted trees in pastures and edges of fields. It is             another synthetic auxin.         -   Triclopyr.

Insecticides

-   -   An insecticide is a pesticide used against insects in all         developmental forms. They include ovicides and larvicides used         against the eggs and larvae of insects. Insecticides are used in         agriculture, medicine, industry and the household. In the         following, suitable insecticides are mentioned:         -   Chlorinated insecticides such as, for example, Camphechlor,             DDT, Hexachlorocyclohexane, gamma-Hexachlorocyclohexane,             Methoxychlor, Pentachlorophenol, TDE, Aldrin, Chlordane,             Chlordecone, Dieldrin, Endosulfan, Endrin, Heptachlor, Mirex             and their mixtures;         -   Organophosphorus compounds such as, for example, Acephate,             Azinphos-methyl, Bensulide, Chlorethoxyfos, Chlorpyrifos,             Chlorpyriphos-methyl, Diazinon, Dichlorvos (DDVP),             Dicrotophos, Dimethoate, Disulfoton, Ethoprop, Fenamiphos,             Fenitrothion, Fenthion, Fosthiazate, Malathion,             Methamidophos, Methidathion, Methyl-parathion, Mevinphos,             Naled, Omethoate, Oxydemeton-methyl, Parathion, Phorate,             Phosalone, Phosmet, Phostebupirim, Pirimiphos-methyl,             Profenofos, Terbufos, Tetrachlorvinphos, Tribufos,             Trichlorfon and their mixture;         -   Carbamates such as, for example, Aldicarb, Carbofuran,             Carbaryl, Methomyl, 2-(1-Methylpropyl)phenyl methylcarbamate             and their mixtures;         -   Pyrethroids such as, for example, Allethrin, Bifenthrin,             Deltamethrin, Permethrin, Resmethrin, Sumithrin,             Tetramethrin, Tralomethrin, Transfluthrin and their             mixtures;         -   Plant toxin derived compounds such as, for example, Derris             (rotenone), Pyrethrum, Neem (Azadirachtin), Nicotine,             Caffeine and their mixtures.

Rodenticides

-   -   Rodenticides are a category of pest control chemicals intended         to kill rodents. Rodents are difficult to kill with poisons         because their feeding habits reflect their place as scavengers.         They would eat a small bit of something and wait, and if they do         not get sick, they would continue eating. An effective         rodenticide must be tasteless and odorless in lethal         concentrations, and have a delayed effect. In the following,         examples for suitable rodenticides are given:         -   Anticoagulants are defined as chronic (death occurs after             1-2 weeks post ingestion of the lethal dose, rarely sooner),             single-dose (second generation) or multiple dose (first             generation) cumulative rodenticides. Fatal internal bleeding             is caused by lethal dose of anticoagulants such as             brodifacoum, coumatetralyl or warfarin. These substances in             effective doses are antivitamins K, blocking the enzymes             K₁-2,3-epoxide-reductase (this enzyme is preferentially             blocked by 4-hydroxycoumarin/4-hydroxythiacoumarin             derivatives) and K₁-quinone-reductase (this enzyme is             preferentially blocked by indandione derivatives), depriving             the organism of its source of active vitamin K₁. This leads             to a disruption of the vitamin K cycle, resulting in an             inability of production of essential blood-clotting factors             (mainly coagulation factors II (prothrombin), VII             (proconvertin), IX (Christmas factor) and X (Stuart             factor)). In addition to this specific metabolic disruption,             toxic doses of 4-hydroxycoumarin/4-hydroxythiacoumarin and             indandione anticoagulants are causing damage to tiny blood             vessels (capillaries), increasing their permeability,             causing diffuse internal bleedings (haemorrhagias). These             effects are gradual; they develop in the course of days and             are not accompanied by any nociceptive perceptions, such as             pain or agony. In the final phase of intoxication the             exhausted rodent collapses in hypovolemic circulatory shock             or severe anemia and dies calmly. Rodenticidal             anticoagulants are either first generation agents             (4-hydroxycoumarin type: warfarin, coumatetralyl; indandione             type: pindone, diphacinone, chlorophacinone), generally             requiring higher concentrations (usually between 0.005 and             0.1%), consecutive intake over days in order to accumulate             the lethal dose, poor active or inactive after single             feeding and less toxic than second generation agents, which             are derivatives of 4-hydroxycoumarin (difenacoum,             brodifacoum, bromadiolone and flocoumafen) or             4-hydroxy-1-benzothiin-2-one (4-hydroxy-1-thiacoumarin,             sometimes incorrectly referred to as             4-hydroxy-1-thiocoumarin, for reason see heterocyclic             compounds), namely difethialone. Second generation agents             are far more toxic than first generation agents, they are             generally applied in lower concentrations in baits (usually             in the order of 0.001-0.005%), and are lethal after single             ingestion of bait and are effective also against strains of             rodents that have become resistant against first generation             anticoagulants; thus the second generation anticoagulants             are sometimes referred to as “superwarfarins”. Sometimes,             anticoagulant rodenticides are potentiated by an antibiotic,             most commonly by sulfaquinoxaline. The aim of this             association (e.g. warfarin 0.05%+sulfaquinoxaline 0.02%, or             difenacoum 0.005%+sulfaquinoxaline 0.02% etc.) is that the             antibiotic/bacteriostatic agent suppresses intestinal/gut             symbiotic microflora that represents a source of vitamin K.             Thus the symbiotic bacteria are killed or their metabolism             is impaired and the production of vitamin K by them is             diminuted, an effect which logically contributes to the             action of anticoagulants. Antibiotic agents other than             sulfaquinoxaline may be used, for example co-trimoxazole,             tetracycline, neomycin or metronidazole. A further synergism             used in rodenticidal baits is that of an association of an             anticoagulant with a compound with vitamin D-activity, i.e.             cholecalciferol or ergocalciferol (see below). A typical             formula used is, e.g., warfarin 0.025-0.05%+cholecalciferol             0.01%. In some countries there are even fixed             three-component rodenticides, i.e.             anticoagulant+antibiotic+vitamin D, e.g. difenacoum             0.005%+sulfaquinoxaline 0.02%+cholecalciferol 0.01%.             Associations of a second-generation anticoagulant with an             antibiotic and/or vitamin D are considered to be effective             even against the most resistant strains of rodents, though             some second generation anticoagulants (namely brodifacoum             and difethialone), in bait concentrations of 0.0025-0.005%             are so toxic that no known resistant strain of rodents             exists and even rodents resistant against any other             derivatives are reliably exterminated by application of             these most toxic anticoagulants.         -   Vitamin K₁ has been suggested and successfully used as an             antidote for pets or humans, which/who were either             accidentally or intentionally (poison assaults on pets,             suicidal attempts) exposed to anticoagulant poisons. In             addition, since some of these poisons act by inhibiting             liver functions and in progressed stages of poisoning,             several blood-clotting factors as well as the whole volume             of circulating blood lacks, a blood transfusion (optionally             with the clotting factors present) can save a person's life             who inadvertently takes them, which is an advantage over             some older poisons.         -   Metal phosphides have been used as a means of killing             rodents and are considered single-dose fast acting             rodenticides (death occurs commonly within 1-3 days after             single bait ingestion). A bait consisting of food and a             phosphide (usually zinc phosphide) is left where the rodents             can eat it. The acid in the digestive system of the rodent             reacts with the phosphide to generate the toxic phosphine             gas. This method of vermin control has possible use in             places where rodents are resistant to some of the             anticoagulants, particularly for control of house and field             mice; zinc phosphide baits are also cheaper than most             second-generation anticoagulants, so that sometimes, in             cases of large infestation by rodents, their population is             initially reduced by copious amounts of zinc phosphide bait             applied, and the rest of the population that survived the             initial fast-acting poison is then eradicated by prolonged             feeding on anticoagulant bait. Inversely, the individual             rodents that survived anticoagulant bait poisoning (rest             population) can be eradicated by pre-baiting them with             nontoxic bait for a week or two (this is important to             overcome bait shyness, and to get rodents used to feeding in             specific areas by offering specific food, especially when             eradicating rats) and subsequently applying poisoned bait of             the same sort as used for pre-baiting until all consumption             of the bait ceases (usually within 2-4 days). These methods             of alternating rodenticides with different modes of action             provides a factual or an almost 100% eradication of the             rodent population in the area if the acceptance/palatability             of bait is good (i.e., rodents readily feed on it).         -   Phosphides are rather fast acting rat poisons, resulting in             that the rats are dying usually in open areas instead of the             affected buildings. Typical examples are aluminum phosphide             (fumigant only), calcium phosphide (fumigant only),             magnesium phosphide (fumigant only) and zinc phosphide (in             baits). Zinc phosphide is typically added to rodent baits in             amounts of around 0.75-2%. The baits have a strong, pungent             garlic-like odor characteristic for phosphine liberated by             hydrolysis. The odor attracts (or, at least, does not             repulse) rodents, but has a repulsive effect on other             mammals; birds, however (notably wild turkeys), are not             sensitive to the smell and feed on the bait thus becoming             collateral damage.         -   Hypercalcemia. Calciferols (vitamins D), cholecalciferol             (vitamin D₃) and ergocalciferol (vitamin D₂) are used as             rodenticides, which are toxic to rodents for the same reason             that they are beneficial to mammals: they are affecting             calcium and phosphate homeostasis in the body. Vitamins D             are essential in minute quantities (few IUs per kilogram             body weight daily, which is only a fraction of a milligram),             and like most fat soluble vitamins they are toxic in larger             doses as they readily result in the so-called             hypervitaminosis, which is, simply said, poisoning by the             vitamin. If the poisoning is severe enough (that is, if the             dose of the toxicant is high enough), it eventually leads to             death. In rodents consuming the rodenticidal bait it causes             hypercalcemia by raising the calcium level, mainly by             increasing calcium absorption from food, mobilising             bone-matrix-fixed calcium into ionised form (mainly             monohydrogencarbonate calcium cation, partially bound to             plasma proteins, [CaHCO₃]⁺), which circulates dissolved in             the blood plasma, and after ingestion of a lethal dose the             free calcium levels are raised sufficiently so that blood             vessels, kidneys, the stomach wall and lungs are             mineralised/calcificated (formation of calcificates,             crystals of calcium salts/complexes in the tissues thus             damaging them), leading further to heart problems (myocard             is sensitive to variations of free calcium levels that are             affecting both myocardial contractibility and excitation             propagation between atrias and ventriculas) and bleeding             (due to capillary damage) and possibly kidney failure. It is             considered to be single-dose, or cumulative (depending on             concentration used; the common 0.075% bait concentration is             lethal to most rodents after a single intake of larger             portions of the bait), sub-chronic (death occurring usually             within days to one week after ingestion of the bait).             Applied concentrations are 0.075% cholecalciferol and 0.1%             ergocalciferol when used alone. There is an important             feature of calciferols toxicology which is that they are             synergistic with anticoagulant toxicants. This means that             mixtures of anticoagulants and calciferols in the same bait             are more toxic than the sum of toxicities of the             anticoagulant and the calciferol in the bait so that a             massive hypercalcemic effect can be achieved by a             substantially lower calciferol content in the bait and             vice-versa. More pronounced anticoagulant/hemorrhagic             effects are observed if calciferol is present. This             synergism is mostly used in baits low in calciferol because             effective concentrations of calciferols are more expensive             than effective concentrations of most anticoagulants. The             historically very first application of a calciferol in             rodenticidal bait was, in fact, the Sorex product Sorexa® D             (with a different formula than today's Sorexa® D) back in             the early 1970's, containing warfarin 0.025%+ergocalciferol             0.1%. Today, Sorexa® CD contains a 0.0025% difenacoum+0.075%             cholecalciferol combination. Numerous other brand products             containing either calciferols 0.075-0.1% (e.g. Quintox®,             containing 0.075% cholecalciferol) alone, or a combination             of calciferol 0.01-0.075% with an anticoagulant are             marketed.

Miticides, Moluscicides and Nematicides

-   -   Miticides are pesticides that kill mites. Antibiotic miticides,         carbamate miticides, formamidine miticides, mite growth         regulators, organochlorine, permethrin and organophosphate         miticides all belong to this category.     -   Molluscicides are pesticides used to control mollusks, such as         moths, slugs and snails. These substances include metaldehyde,         methiocarb and aluminium sulfate. A nematicide is a type of         chemical pesticide used to kill parasitic nematodes (a phylum of         worm).     -   A nematicide is obtained from a neem tree's seed cake; which is         the residue of neem seeds after oil extraction. The neem tree is         known by several names in the world but was first cultivated in         India since ancient times.

Antimicrobials

-   -   In the following examples, antimicrobials suitable for         agrochemical compositions according to the present invention are         given. Bactericidal disinfectants mostly used are those applying         -   active chlorine (i.e., hypochlorites, chloramines,             dichloroisocyanurate and trichloroisocyanurate, wet             chlorine, chlorine dioxide, etc.),         -   active oxygen (peroxides such as peracetic acid, potassium             persulfate, sodium perborate, sodium percarbonate and urea             perhydrate),         -   iodine (iodpovidone (povidone-iodine, Betadine), Lugol's             solution, iodine tincture, iodinated nonionic surfactants),         -   concentrated alcohols (mainly ethanol, 1-propanol, called             also n-propanol and 2-propanol, called isopropanol and             mixtures thereof; further, 2-phenoxyethanol and 1- and             2-phenoxypropanols are used),         -   phenolic substances (such as phenol (also called “carbolic             acid”), cresols (called “Lysole” in combination with liquid             potassium soaps), halogenated (chlorinated, brominated)             phenols, such as hexachlorophene, triclosan,             trichlorophenol, tribromophenol, pentachlorophenol, Dibromol             and salts thereof),         -   cationic surfactants such as some quaternary ammonium             cations (such as benzalkonium chloride, cetyl             trimethylammonium bromide or chloride,             didecyldimethylammonium chloride, cetylpyridinium chloride,             benzethonium chloride) and others, non-quarternary compounds             such as chlorhexidine, glucoprotamine, octenidine             dihydrochloride, etc.),         -   strong oxidizers such as ozone and permanganate solutions;         -   heavy metals and their salts such as colloidal silver,             silver nitrate, mercury chloride, phenylmercury salts,             copper sulfate, copper oxide-chloride etc. Heavy metals and             their salts are the most toxic and environmentally hazardous             bactericides and, therefore, their use is strongly             suppressed or forbidden.             -   Further, also         -   properly concentrated strong acids (phosphoric, nitric,             sulfuric, amidosulfuric, toluenesulfonic acids) and         -   alkalis (sodium, potassium, calcium hydroxides), at pH<1             or >13, respectively, particularly at elevated temperatures             (above 60° C.) kill bacteria.     -   As antiseptics (i.e., germicide agents that can be used on human         or animal body, skin, mucoses, wounds and the like), few of the         above mentioned disinfectants can be used under proper         conditions (mainly concentration, pH, temperature and toxicity         toward man/animal). Among them, important are         -   Some properly diluted chlorine preparations (e.g. Daquin's             solution, 0.5% sodium or potassium hypochlorite solution,             pH-adjusted to pH 7-8, or 0.5-1% solution of sodium             benzenesulfochloramide (chloramine B)), some         -   iodine preparations such as iodopovidone in various galenics             (ointments, solutions, wound plasters), in the past also             Lugol's solution,         -   peroxides as urea perhydrate solutions and pH-buffered             0.1-0.25% peracetic acid solutions,         -   alcohols with or without antiseptic additives, used mainly             for skin antisepsis,         -   weak organic acids such as sorbic acid, benzoic acid, lactic             acid and salicylic acid         -   some phenolic compounds such as hexachlorophene, triclosan             and Dibromol, and         -   cation-active compounds such as 0.05-0.5% benzalkonium,             0.5-4% chlorhexidine, 0.1-2% octenidine solutions.     -   Bactericidal antibiotics kill bacteria; bacteriostatic         antibiotics only slow down their growth or reproduction.         Penicillin is a bactericide, as are cephalosporins.         Aminoglycosidic antibiotics can act in both a bactericidic         manner (by disrupting cell wall precursor leading to lysis) or         bacteriostatic manner (by connecting to 30 s ribosomal subunit         and reducing translation fidelity leading to inaccurate protein         synthesis). Other bactericidal antibiotics according to the         present invention include the fluoroquinolones, nitrofurans,         vancomycin, monobactams, co-trimoxazole, and metronidazole.         Emulsifiers

In a number of cases it is advantageous to add emulsifiers (component c) to the biocide compositions in order to support the stability of the products. A first preferred group of emulsifiers encompasses non-ionic surfactants such as, for example:

-   -   products of the addition of 2 to 30 mol ethylene oxide and/or 0         to 5 mol propylene oxide onto linear or branched, saturated or         unsaturated C₈₋₂₂ fatty alcohols, onto C₁₂₋₂₂ fatty acids and         onto alkyl phenols containing 8 to 15 carbon atoms in the alkyl         group;     -   C_(12/18) fatty acid monoesters and diesters of addition         products of 1 to 30 mol ethylene oxide onto glycerol;     -   glycerol mono- and diesters and sorbitan mono- and diesters of         saturated and unsaturated fatty acids containing 6 to 22 carbon         atoms and ethylene oxide addition products thereof;     -   addition products of 15 to 60 mol ethylene oxide onto castor oil         and/or hydrogenated castor oil;     -   polyol esters and, in particular, polyglycerol esters such as,         for example, polyglycerol polyricinoleate, polyglycerol         poly-12-hydroxystearate or polyglycerol dimerate isostearate.         Mixtures of compounds from several of these classes are also         suitable;     -   addition products of 2 to 15 mol ethylene oxide onto castor oil         and/or hydrogenated castor oil and/or other vegetable oils;     -   partial esters based on linear, branched, unsaturated or         saturated C_(6/22) fatty acids, ricinoleic acid and         12-hydroxystearic acid and glycerol, polyglycerol,         pentaerythritol, dipentaerythritol, sugar alcohols (for example         sorbitol), alkyl glucosides (for example methyl glucoside, butyl         glucoside, lauryl glucoside) and polyglucosides (for example         cellulose);     -   mono-, di and trialkyl phosphates and mono-, di- and/or         tri-PEG-alkyl phosphates and salts thereof;     -   wool wax alcohols;     -   polysiloxane/polyalkyl polyether copolymers and corresponding         derivatives;     -   mixed esters of pentaerythritol, fatty acids, citric acid and         fatty alcohol and/or mixed esters of C₆₋₂₂ fatty acids, methyl         glucose and polyols, preferably glycerol or polyglycerol,     -   polyalkylene glycols and     -   alkyl and glycerol carbonates.

The addition products of ethylene oxide and/or propylene oxide onto fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or onto castor oil are known commercially available products. They are homologue mixtures of which the average degree of alkoxylation corresponds to the ratio between the quantities of ethylene oxide and/or propylene oxide and substrate with which the addition reaction is carried out. C_(12/18) fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are known as lipid layer enhancers for cosmetic formulations. The preferred emulsifiers are described in more detail as follows:

Partial Glycerides

Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric acid diglyceride, malic acid monoglyceride, malic acid diglyceride and technical mixtures thereof which may still contain small quantities of triglyceride from the production process. Addition products of 1 to 30 mol, and preferably 5 to 10 mol ethylene oxide onto the partial glycerides mentioned are also suitable.

Sorbitan Esters

Suitable sorbitan esters are sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof. Addition products of 1 to 30 mol, and preferably 5 to 10 mol ethylene oxide onto the sorbitan esters mentioned are also suitable.

Polyglycerol Esters

Typical examples of suitable polyglycerol esters are Polyglyceryl-2 Dipolyhydroxystearate (Dehymuls® PGPH), Polyglycerin-3-Diisostearate (Lameform® TGI), Polyglyceryl-4 Isostearate (Isolan® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403), Polyglyceryl Dimerate Isostearate and mixtures thereof. Examples of other suitable polyolesters are the mono-, di- and triesters of trimethylol propane or pentaerythritol with lauric acid, cocofatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like, optionally reacted with 1 to 30 mol ethylene oxide.

Typical anionic emulsifiers are aliphatic C₁₂₋₂₂ fatty acids such as palmitic acid, stearic acid or behenic acid, for example, and C₁₂₋₂₂ dicarboxylic acids such as azelaic acid or sebacic acid for example.

Other suitable emulsifiers are zwitterionic surfactants. Zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Ampholytic surfactants are also suitable emulsifiers. Ampholytic surfactants are surface-active compounds which, in addition to a C_(8/18) alkyl or acyl group, contain at least one free amino group and at least one —COOH— or —SO₃H— group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C_(12/18) acyl sarcosine.

Biocide Compositions

Typically, the compositions according to the present invention comprise

-   (a) about 0.1% b.w. to about 99% b.w., preferably about 5% b.w. to     about 90% b.w., and most preferably about 15% b.w. to about 25%     b.w., dialkylamides derived from hydroxycarboxylic acids, -   (b) about 1% b.w. to about 99.1% b.w., preferably about 2% b.w. to     about 80% b.w., and most preferably about 5% b.w. to about 15% b.w.,     biocides, and -   (c) 0% b.w. to about 10% b.w., and preferably 1 to 5% b.w.,     emulsifiers     on condition that the amounts add with water to 100% b.w. Usually,     the active matter content (which means the sum of components a+b+c)     is about 5% b.w. to about 50% b.w., and preferably about 10% b.w. to     about 25% b.w., calculated on the total of the aqueous composition.

INDUSTRIAL APPLICATION

A final embodiment of the present invention relates to the use of dialkylamides based on hydroxycarboxylic acids, in particular of the dimethylamide of lactic acid as solvents or dispersants for biocides.

EXAMPLES Examples 1 to 6, Comparative Examples C1 and C2

Several aqueous concentrates were prepared by mixing biocides, dimethylamides and emulsifiers in water until a homogenous solution was obtained. The concentrates were subsequently diluted with water in order to achieve an active matter concentration of 10% b.w. The products thus obtained were stored over a period of 10 to 40 days at temperatures of 5, 20 and 40° C. The stability of the mixtures was observed by inspection and determined according to the following scale: (++)=stable; (+)=slight phase separation/formation of some crystals; (o)=significant phase separation/sedimentation; (−) phases clearly separated/strong sedimentation of crystals. The results are compiled in Table 1. The amounts reflect the composition of the concentrates.

TABLE 1 Stability of biocide compositions Composition [% b.w.] 1 2 3 4 5 6 C1 C2 Biphenyl 35 — — — — — — — Glyphosphate — — — — 25 — 35 — Deltametrin — — 35 — — 25 — 35 Glucoprotamin — — — 35 — — — — Lactic acid dimethylamide 25 25 25 25 15 15 — — Stearic acid dimethylamide — — — — — — 25 25 Sorbitanmono/dilaurate + 20EO 10 10  5  5 — — — — Polyglyceryl-2 — —  5  5 10 10 — — Dipolyhydroxystearate Water add to 100 Stability after 10 days, 5° C. ++ ++ ++ ++ ++ ++ ◯ ◯ after 20 days, 5° C. + + ++ ++ ++ ++ − − after 40 days, 5° C. ◯ ◯ + + + ++ − − after 10 days, 20° C. ++ ++ ++ ++ ++ ++ ++ ++ after 20 days, 20° C. ++ ++ ++ ++ ++ ++ ++ ++ after 40 days, 20° C. ++ ++ ++ ++ ++ ++ + + after 10 days, 40° C. ++ ++ ++ ++ ++ ++ + + after 20 days, 40° C. ++ ++ ++ ++ ++ ++ ◯ ◯ after 40 days, 40° C. + + + + ++ ++ ◯ ◯ 

1. A biocide composition comprising: (a) at least one dialkylamide of a hydroxycarboxylic acid selected from the group consisting of lactic acid, ricinoleic acid, 12-hydroxy stearic acid and mixtures thereof, wherein at least one alkyl group of the dialkylamide has 1 to 4 carbon atoms, and (b) at least one biocide selected from the group consisting of herbicides, insecticides, rodenticides, miticides, moluscicides, nematicides and combinations thereof.
 2. The composition of claim 1 wherein component (a) comprises lactic acid dimethylamide.
 3. The composition of claim 1 further comprising as component (c) at least one emulsifier.
 4. The composition of claim 1, wherein the composition has a mean storage time of at least 4 weeks at temperatures between 5 and 40° C. without phase separation or sedimentation.
 5. The composition of claim 1, wherein the composition is effective to reduce formation of crystals during storage.
 6. A biocide composition comprising: (a) 0.1% to 99% by weight, based on the composition, of at least one dialkylamide of a hydroxycarboxylic acid selected from the group consisting of lactic acid, ricinoleic acid, 12-hydroxy stearic acid and mixtures thereof, wherein at least one alkyl group of the dialkylamide has 1 to 4 carbon atoms, (b) 1% to 99.1% by weight, based on the composition, of at least one biocide, and (c) 0% to 10% by weight, based on the composition, of at least one emulsifier, provided that the amounts, including water, total 100%.
 7. The composition of claim 6 wherein the sum of components (a)+(b)+(c) equals 5% to 50% by weight, based on the composition.
 8. A method of dissolving or dispersing biocides selected from the group consisting of herbicides, insecticides, rodenticides, miticides, moluscicides, nematicides, and combinations thereof, the method comprising adding at least one dialkylamide of a hydroxycarboxylic acid selected from the group consisting of lactic acid, tartaric acid, ricinoleic acid, 12-hydroxy stearic acid and mixtures thereof to aid in dissolving or dispersing at least one biocide, wherein at least one alkyl group of the dialkylamide has 1 to 4 carbon atoms. 